Process of making wet strength paper containing mono primary polyamine and organic dihalide modified, epoxidized polyamide

ABSTRACT

Cationic extended terminated polyamide resins are prepared which exhibit highly desirable paper wet strength properties.

This is a continuation of application Ser. No. 401,386, filed Sept. 27,1973, now abandoned which is a divisional of application Ser. No.304,729, filed Nov. 8, 1972, now U.S. Pat. No. 3,703,279.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to cationic extended terminated polyamide resins,their preparation, and their use for increasing the wet strength ofpaper. Relevant United States classes appear to be 162/164, 260/29.2 and260/78.

2. Description of the Prior Art

The closest known prior art are U.S. Pat. Nos. 2,926,116; 2,926,154;3,125,552; 3,535,288; and 3,645,954; and French Pat. No. 884,271 (whichcorresponds to Belgian Pat. No. 446,643).

U.S. Pat. No. 2,926,116 discloses a paper wet strength resin that isuncured, thermosetting, and cationic, and which comprises awater-soluble polymeric reaction product of epichlorohydrin and apolyamide derived from a polyalkylene polyamine and a saturatedaliphatic dibasic carboxylic acid containing from 3 to 10 carbon atoms.

U.S. Pat. No. 2,926,154 is a continuation-in-part of U.S. Pat. No.2,926,116 and differs essentially in that the polyalkylene polyaminescontain two primary amine groups and at least one secondary amine group,and the preferred saturated aliphatic dibasic carboxylic acids are thosehaving from 3 to 8 carbon atoms, plus diglycolic acid.

U.S. Pat. No. 3,125,552, discloses a paper wet strength resin whichcomprises a water-soluble polymeric reaction product of epichlorohydrinand a polyamide derived from a polyalkylene polyamine having at leasttwo primary amine groups and at least one secondary amine group, and anunsaturated polycarboxylic acid having at least one carbon to carbondouble bond.

U.S. Pat. No. 3,535,288 discloses a paper wet strength resin whichcomprises a polyamide, which is the reaction product of an aminocarboxylate and a polyalkylene polyamine, and which is then reacted withepichlorohydrin.

U.S. Pat. No. 3,645,954 discloses a paper wet strength resin which ismade by reacting an aliphatic dicarboxylic acid with a polyalkyleneamine, reacting the resulting polyamide with a lactam, and then reactingthe resulting block copolyamide with epichlorohydrin.

French Pat. No. 884,271 discloses a resin for improving paper, interalia, which comprises the reaction product of epichlorohydrin with anamine, which is then further reacted with a compound containing areactive hydrogen atom, such as certain carboxylic acids, alcohols, oramines; as well as the epoxidation of a polyamide produced from apolyamine and an acid ester.

SUMMARY OF THE INVENTION

This invention comprises cationic polyamides which have highly desirablewet strength properties and which exhibit excellent stability at higherconcentrations. The general procedure for synthesis of these resins isas follows:

1. An acid is reacted with a backbone polyamine to form a "basepolyamide" with terminal carboxylic groups;

2. The base polyamide is reacted with a terminating polyamine to form a"terminated base" (polyamide) with terminal secondary and/or tertiaryamino groups;

3. The terminated base is reacted with a chain extender to form an"extended base"; and then

4. The extended base is reacted with an epoxidizing agent to form an"epoxidized base," which is the completed wet strength resin.

The resin is added to paper pulp or preformed paper to increase the wetstrength of the finished paper. Wet-strength paper is produced byincorporating in paper during its manufacture from about 0.1 to about5.0 percent by dry weight of the resins of the present invention basedon the dry weight of the pulp present in the paper and thereafter curingthe resins in the paper to a water-insoluble state, thereby producing awet-strength paper. The preferred point of addition is after the pulphas reached a refined stage. The resin in the paper can be cured byheating the paper containing the resin at from about 80° to about 120°C. for from about 0.5 to about 30 minutes. Paper produced with theresins of this invention has improved wet-strength. Desirable propertiesexhibited by using the resins of this invention and/or paper treatedtherewith include rapid curing, easy repulpability, non-foamingtendencies, low sizing, good rewetting, rapid pulp drainage andexcellent machine performance. Additionally, the resins are very stableand exhibit long shelf-life.

DESCRIPTION OF THE PREFERRED EMBODIMENTS 1. REACTANT COMPONENTS

The acids useful in this invention can be individual acids or mixturesof acids and include:

a. saturated dicarboxylic acids having 4 to 12 carbon atoms;

b. non-decarboxylating unsaturated dicarboxylic acids having from 5 to12 carbon atoms;

c. saturated and non-decarboxylating unsaturated tricarboxylic acidshaving 6 to 10 carbon atoms;

d. C₁₋₁₂ alkyl mono- and di-esters of saturated and unsaturateddicarboxylic acids having 2 to 12 carbon atoms;

e. C₁₋₁₂ alkyl mono- and di-esters of saturated and unsaturatedtricarboxylic acids having 6 to 10 carbon atoms; and

f. anhydrides of saturated and unsaturated dicarboxylic acids having 4or 5 carbon atoms.

Useful and preferred acids utilized in the Examples of this invention,infra, are:

    __________________________________________________________________________    1.                                                                              Acids containing 2 carbon atoms:                                                                 diethyloxalate                                           2.                                                                              Acids containing 3 carbon atoms:                                                                 diethylmalonate                                          3.                                                                              Acids containing 4 carbon atoms:                                                                 succinic acid, succinic                                                       anhydride, diethylsuccinate,                                                  monomethyl succinate, maleic                                                  anhydride, D,L-malic acid                                4.                                                                              Acids containing 5 carbon atoms:                                                                 glutaric acid, glutaric                                                       anhydride, dimethylglutarate,                                                 itaconic acid                                            5.                                                                              Acids containing 6 carbons:                                                                      adipic acid, monomethyl                                                       adipate                                                  6.                                                                              Acids containing 7 carbon atoms:                                                                 pimelic acid                                             7.                                                                              Acids containing 8 carbon atoms:                                                                 suberic acid                                             8.                                                                              Acids containing 9 carbon atoms:                                                                 azelaic acid                                             9.                                                                              Acids containing 10 carbon atoms:                                                                sebacic acid                                             __________________________________________________________________________

A useful and preferred acid not utilized in the examples of thisinvention is diglycollic acid.

A useful acid which is not preferred, and which was utilized in Example43 of this invention, is citric acid.

Other acids which may be utilized in this invention include, but are notlimited to, methylmaleic acid, dibutyl α-ketoglutarate, diethylβ-ketoglutarate, tricarballylic acid, 3,4-hexadiendioic acid, hexylpimelate, didecyl suberate, methyl octyl azelate, didodecyl sebacate,undecandioic acid, dodecandioic acid, 4-octenedioic acid, and the like.

The preferred acids may be used either alone or in combination withother acids. Acids which are not preferred may be used alone only if theresulting resin has a wet strength of at least 14 percent. Where theresulting resin using a particular acid has a wet strength of from 10percent up to but not including 14 percent, that acid may be used onlyin combination with a preferred acid, so that the resin resulting fromthe comgination of acids has a wet strength of at least 14 percent. Anacid whose resulting resin has a wet strength of under 10 percent is notconsidered to be within the scope of this invention. [See "Testing ofWet Strength Efficacy", infra.]

The backbone polyamines useful in this invention can be any one or amixture of polyamines, branched or straight chain, provided that theycontain at least 2 primary amines which may be located anywhere on thechain and at least one secondary or tertiary amine which also may belocated anywhere on the chain. Examples of preferred backbone polyaminesinclude, but are not limited to: prim, sec-diethylenetriamine; prim,sec-tetraethylenepentamine; prim, tert-bis(aminopropyl) methylamine;prim, sec-pentaethylenehexamine; and prim, sec-triethylenetetramine.Other useful backbone amines include: prim, sec-imino-bis-propylamine;prim, sec-dibutylenetriamine; prim, sec-tetrapropylenepentamine; prim,sec-imino-bis-hexylamine; and prim, tert-bis(aminoethyl) propylamine.

The terminating polyamines useful in this invention can be any one or amixture of polyamines, branched or straight chain, provided that theycontain only one primary amine which may be located anywhere on thechain and at least one secondary or tertiary amine which also may belocated anywhere on the chain.

Examples of preferred terminating amines include, but are not limitedto: prim, tert-dimethylaminopropylamine; and prim,sec-N-aminoethylethanolamine. Other useful terminating amines include:prim, tert-diethylaminoethylamine; prim,tert-methylbutylaminopropylamine; and prim,sec-aminoethylisopropanolamine.

The chain extenders useful in this invention can be any one or a mixtureof alkyl dihalide, alkyl ether dihalide, phenyl bis(alkyl halide), andphenyl alkyl dihalide containing from 1 to 12 carbon atoms.

Examples of preferred useful chain extenders include, but are notlimited to, methylenedibromide, ethylenedibromide, methylmediiodide,dichloroethylether, dichloroisopropylether, and triglycol dichloride.Other useful chain extenders include phenyl bis(methyl chloride), phenylbutyl dibromide, and the like.

As used in this invention, the term "epoxidizing agent" means an epoxycompound used to cap amine groups on the extended base. The epoxidizingagents useful in this invention can be any one or a mixture ofepihalohydrin and alkyl substituted epihalohydrin. Examples of usefulepoxidizing agents are epichlorohydrin, epibromohydrin, epiiodohydrin,epifluorohydrin, bromoepoxybutane, chloroepoxyhexane,iodoepoxyisobutane, and the like. Preferred epoxidizing agents areepichlorohydrin and epibromohydrin.

2. REACTANT PARAMETERS

The proportions of the chemicals used in the synthesis of the wetstrength resin are as follows.

In the formation of the base polyamide, the mole ratio of the backboneamine to the acid must always be less than 1 to 1. The maximum range ofmolar ratio is about 0.66 to about 0.99:1 and the preferred range isabout 0.75 to about 0.95:1. It is critical that fewer moles of thebackbone polyamine be present than of the acid, so that the basepolyamide has free carboxylic groups remaining, thus permitting reactionwith the terminating amine.

The base polyamide is reacted with at least sufficient terminatingpolyamine to cap all free carboxylic groups remaining. It is preferredto use a slight excess of terminating polyamine to ensure completecapping of the base polyamide.

The terminated base is reacted with the chain extender in approximatelyequimolar quantities.

The extended base is reacted with from about 0.6 moles to about 1.5moles of epoxidizing agent (and preferably about 1.0 to about 1.4 moles)per unreacted secondary or tertiary amine remaining on the extendedbase, with the proviso that the amount of epoxidizing agent is notsufficiently in excess to reduce the pH of the reaction medium belowabout 5, as a result of hydrolysis.

There is no limitation to the length or molecular weight of thecompleted polymer, except that the wet strength resin must be soluble inwater or capable of forming a colloidal dispersion. The presence oflarge numbers of epoxidized amino groups will permit very largepolymers, (for example, a polymer having a molecular weight of 40,000where the amino groups on the backbone are separated by not more than 6consecutive carbon atoms).

One of the great advantages of this invention is that a highconcentration (percentage) of active material can be produced. This isdone by reducing the amount of water added when extending the terminatedbase or when epoxidizing the extended base. If a reduced amount of wateris added, the reaction temperature must also be reduced and the reactiontime may be lengthened. Because the polymers of this invention are stillreactive and are thermosetting, it is not possible to increase thepercentage of active material by conventional drying methods. Therefore,the water added during the synthesis and pH adjustment remains with theresin and comprises at least 30 parts by weight per 70 parts by weightof resin, in the final product. A high percentage of active material isvery desirable as it reduces transportation costs and increases ease ofhandling.

Normal temperature parameters are: from about 120° to about 240° C forformation of the base polyamide; from about 120° to about 180° C forformation of the terminated base; from about 100° to about 120° C forformation of the extended base; and from about 40° to about 90° C forformation of the epoxidized base.

Exceptions to the normal temperature parameters are required when usingacids containing five carbon atoms, diesters, esters of decarboxylatingacids, and hydroxy acids. Where exceptions to temperature parameters arenot given below, further reactions in the sequence are run at the normaltemperature parameters. Where the acid used requires conflictingexceptions, the lower temperature range should be used.

Acids containing five carbon atoms are reacted at from about 120° toabout 175° C for formation of the base polyamide and from about 120° toabout 170° C for formation of the terminated base. Further reactions inthe sequence are run at normal temperature parameters. The reduction ofthe upper temperature parameters is dictated by the tendency of acidscontaining five carbon atoms to form insoluble cyclic polymers.

Diesters are reacted at normal minimum temperatures of about 80° C andat maximum temperatures of either the reflux temperature of thealcohol/resin mixture, or the temperature at which the resin polymerdegrades, whichever is lower, for formation of the base polyamide. Thesetemperatures also apply to formation of the terminated base and theextended base. The alcohol referred to above is the by-product of theformation of the base polyamide (see "Preparation of the Resin," infra)and its nature will depend on the diester used. For example, using adimethyl ester will produce methyl alcohol, using an ethylhexyl esterwill produce ethyl alcohol and hexyl alcohol, and using a didodecylester will produce dodecyl alcohol. Of course, if the alcohol is removedfrom the base polyamide, the temperature limitations will not apply tothe further reactions in the sequence.

Esters of decarboxylating acids are reacted at lower temperatures asthey are less stable than the esters of non-decarboxylating acids.Oxalic acid esters are reacted at from about 15° to about 25° C forformation of the base polyamide, at from about 70° to about 90° C forformation of the terminated base, at from about 70° to about 90° C forformation of the extended base, and at from about 40° to about 70° C forformation of the epoxidized base. Maleic acid esters are reacted at fromabout 80° to about 160° C for formation of the base polyamide, at fromabout 80° to about 100° C for formation of the terminated base, and atfrom about 80° to about 100° C for formation of the extended base.

Hydroxy acids usually are reacted at lower temperatures as they usuallyare less stable than the corresponding non-hydroxy acids. D,L-Malic acid(hydroxy succinic acid) is reacted at from about 120° to about 155° Cfor formation of the base polyamide and at from about 100° to about 120°C for formation of the terminated base.

Reaction time parameters are: about 1 to 6 l hours for formation of thebase polyamide; about 15 minutes to 3 hours for formation of theterminated base; about 1 to 3 hours for formation of the extended base;and about 20 minutes to 15 hours for epoxidation to form the wetstrength resin. A notable exception to the above parameters are oxalicacid esters which require about 5 hours to about 20 hours for formationof the base polyamide. The reaction time in a given instance will dependupon the temperature at which the reaction is conducted. A highertemperature will require a shorter reaction time. It should further benoted that these time parameters only apply once the desired reactiontemperature has been reached.

If the resins of this ivnention are prepared with reactant or processparameters outside the above, an insoluble gel may result.

3. PREPARATION OF THE RESIN

The wet strength resins of this invention can be prepared by utilizingthe parameter givenn in the examples with the following procedure,unless otherwise noted.

1. Preparation of the Base Polyamide

a. If an acid or anhydride is used, it is first charged into a reactionvessel and then mixed with at least sufficient water to produce auniform slurry. The backbone polyamine is then added and the mixture isagitated until uniform. An exothermic reaction results. Heat is thenapplied, accompanied by stirring, until a uniform solution results. Theheating is continued until it reaches the highest desired temperaturewhile most of the water is removed by distillation. This includes bothadded water and water formed by the reaction. The heating is furthercontinued at the same temperature and a vacuum is applied until allremaining water is removed.

b. If an ester which is liquid is used, no water is added. The ester ischarged into a reaction vessel and the backbone polyamine is then added,accompanied by agitation until a uniform solution is produced. Either anexothermic or an endothermic reaction will result, depending upon theester chosen. Generally, an unsatured acid ester will produce anexothermic reaction and a saturated acid ester will produce anendothermic reaction. An exception is oxalic acid esters, which produceexothermic reactions. The reaction vessel is then heated to the desiredtemperature and maintained at that temperature for the desired time,under continual agitation. An alcohol will be produced as a reactionby-product if the ester is a diester. If the ester is a mono-ester, bothalcohol and water will be produced. The alcohol from a diester may beallowed to remain or can be removed by distillation. The alcohol/watermixture from a mono-ester must be removed, as water cannot be allowed toremain.

c. If an ester which is sold is used, the ester is first charged into areaction vessel and then heated until it is melted. The melted ester isthen treated as if it were a liquid ester and the above procedure isfollowed.

d. An exception to the above are esters of oxalic acid. These esters arecharged into a reaction vessel to which is first added a water-misciblealcohol with agitation, in order to form an alcohol solution. The basepolyamine is then added to the alcohol solution accompanied byagitation. As an exothermic reaction results, the vessel is cooled inorder not to exceed the desired temperature (see Example 1, Table Ia,infra).

2. Preparation of the Terminated Base To the vessel containing the basepolyamide prepared above, is added a terminating amine. Agitation ismaintained throughout this reaction. The vessel is then heated to thedesired temperature. While the vessel is maintained at the desiredtemperature, a vacuum is applied until any excess of unreactedterminating polyamine is removed.

3. Preparationn of the Extended Base To the vessel containing theterminated base is charged water at least sufficient to make a uniformsolution. The amount of water will depend upon the desired percentage ofactive material in the final product. Thus, a lower amount of water willresult in a more active final product. Agitation is maintainedthroughout this reaction. The chain extender is added and the mixture isthen heated to the desired temperature.

4. Preparation of the Epoxidized Base To the vessel containing theextended base is charged additional water in an amount depending on thedesired concentration of the final product. Agitation is maintainedthroughout this reaction. An epoxidizing agent is then added in thedesired amount and dissolved. The solution is then heated to the desiredtemperature and maintained at that temperature until the reaction iscomplete. Completeness of the reaction may be determined by an increasein viscosity measured by any conventional viscometer. A recordingviscometer is preferred, in order to permit continual monitoring of thereaction. The preferred viscosity is just below the gelation point.

5. Preparation of the Final Product To the vessel containing theepoxidized base is added water in an amount sufficient to reduce theconcentration of active material to the desired level and an acid suchas hydrochloric, sulfuric, nitric, phosphoric, formic, or acetic, in anamount sufficient to reduce the pH to from about 1.0 to 5.5. All of thisis accompanied by continual agitation.

Where the phrases "desired amount," "desired temperature," "desiredtime," etc. are used, they are intended to refer to the values given inthe "Reaction Parameters," supra, or to the values for any givenexample, infra.

4. USE OF THE RESIN FOR INCREASING WET STRENGTH

The resins of this invention are used in paper-making to increase thewet-strength of paper. These resins can be applied to appear or otherfelted cellulosic products by beater, tub, spray application or thelike. A preferred method of incorporating these resins in paper isinternal addition of the resin to the pulp prior to sheet formation totake advantage of the substantivity of the resins for hydratedcellulosic fibers. In practicing this method of application, an aqueoussolution of the resin in its uncured and hydrophilic state is added toan aqueous suspension of paper stock in the beater, stock chest, Jordan,fan pump, head box, or other suitable point, before sheet formation.About 0.1 to about 5.0 parts by weight of dry resin (and preferablyabout 0.5 parts to about 1.5 parts by weight) based on 100 parts byweight of dry pulp are added to the aqueous suspension of paper stock.The quantity of resin added to the aqueous stock suspension will dependon the degree of wet-strength desired in the finished paper and on theamount of resin retained by the paper fibers. Paper sheet is then formedfrom the paper stock containing the resins and heated at about 80° toabout 120° C. for from about 0.5 to about 30 minutes to cure the resinin the paper to a polymerized water-insoluble state which impartswet-strength to the paper sheet.

These resins can also be applied to preformed partially or completelydried paper by spraying, impregnating, immersing, coating, or othersuitable methods for application of aqueous solutions to these resins inpaper making. Application and curing is then effected in the sameamounts and manner as if the resin were incorporated in the pulp.

The resins of this invention can be cured under acid, neutral oralkaline conditions, e.g., at a pH of from about 4.0 to about 10.0, andpreferably about 7.0 to about 9.0, (see Table III, infra). Optimumresults can be achieved with these results under the neutral or alkalineapplication and curing conditions which frequently exist in papermaking. Since extensive corrosion of equipment occurs under acidconditions, it is an advantage that acid conditions are not required.Paper produced with these resins has greatly improved wet-strength. Asdefined herein, "paper" includes paper towels, absorbent tissues, filterpapers, paper for resin saturation, and the lie, as well as heavierstocks such as wrapping paper, bag paper, paperboard corrugatedcontainers, and the like.

5. TESTING OF WET STRENGTH EFFICACY

The standard used herein and in the paper industry for a wet strengthresin is that based upon a paper written by K. W. Britt which appearedin the April, 1944 issue of "The Paper Industry and Paper World" at page37. According to that article, a wet strength paper may be defined asbeing a paper in which the wet tensile strength is at least 15 percentof the dry tensile strength. In view of the fact that the reactantcomponents used to make the wet strength resins of this invention may bemixtures, and allowing for experimental error, it is considered that aresin achieving 14 percent or higher wet strength is adequate. It ispossible to use mixtures of resins having from 10 up to 14 percent wetstrength with resins having over 14 percent wet strength, provided thatthe mixture has a wet strength of at least 14 percent. It is alsopossible to use resins synthesized from mixtures of preferred andnonpreferred acids provided that the resulting resin has a wet strengthof at least 14 percent. (See "Reactant Components," supra). Suchmixtures may be desirable due to considerations such as the cost of thebase chemicals or the ease of production.

The resin was tested as follows. Handsheets of paper were prepared in aconventional manner according to TAPPI procedures using 100 ml. of 2percent consistency unbleached kraft pulp (2 g. dry weight) with 1, 2, 4or 6 ml. additions of a 1 percent by weight solution of the resins ofExamples 1 through 68, that is, 0.5, 1.0, 2.0 or 3.0 percentrespectively by weight of dry resin based on the weight of dry pulp.

Samples of the above handsheets were then cured, and tested according toTAPPI test procedures T 456 m-49 and T 404 ts-66. The wet strengthsobtained using these tests are shown in the column headed "% WetStrength" in Tables I and II.

6. EXAMPLES AND TEST RESULTS Tables I, Ia, and Ib

The following tables contain summaries of the preparation and wetstrength test results of 49 resins. All of these were prepared accordingto the procedure stated in "Preparation of the Resin," supra, but all ofthem are not within the scope of the invention. All resins having a "%Wet Strength" of at least 10% at either a 0.5%, 1.0%, 2.0% or a 3.0%concentration are considered to be within the scope of this invention.Resins having a wet strength of at least 14% at either a 0.5%, 1.0%,2.0% or a 3.0% concentration are preferred. Table Ia has the temperatureparameters for the examples of Table I, both that of the actualsynthesis and of the acceptable range. Table Ib has actual gramquantities of reactants and reactant times for all of the examples ofTable I. The key to the footnotes in Tables I and Ib will be found afterTable IIb.

                                      TABLE I                                     __________________________________________________________________________                                                   Mole                                                                      V.  Ratio                                     II. Backbone                                                                              Mole                                                                             III. Terminating Epoxi-                                                                            V/      % Wet Strength         Ex.        polyamine   Ratio                                                                            Polyamine                                                                              IV. Chain                                                                             dizing                                                                            active                                                                            %   0.5%                                                                              1.0%               No.                                                                              I. Acid (prim, sec, tert)                                                                         II/I                                                                             (prim, sec, tert)                                                                      Extender                                                                              Agent                                                                             NH  Active                                                                            added                                                                             added              __________________________________________________________________________     1 Diethyl Triethylenetetramine                                                                      0.9                                                                              Dimethylamino-                                                                         Dichloroethyl                                                                         1   1.26                                                                              39.5                                                                              16.0                                                                              21.1                  Oxalate (1,2)          propylamine (1,3)                                                                      ether                                       2 Oxalic Acid                                                                           Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.16                                                                              30.0                                                                               2.1                                                                               2.3                  11      (1,2)          propylamine (1,3)                                                                      ether                                       3 Malonic Acid                                                                          Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Triglycol                                                                             1   1.14                                                                              25.0                                                                               1.9                                                                               1.9                  11      (1,2)          propylamine (1,3)                                                                      dichloride                                  4 Malonic Acid                                                                          Tetraethylenepenta-                                                                       0.95                                                                             Dimethylamino-                                                                         Triglycol                                                                             1   0.84                                                                              21.5                                                                               3.3                                                                               4.4                  11      mine (1,2)     propylamine (1,3)                                                                      dichloride                                  5 Diethyl Diethylenetriamine                                                                        0.94                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.15                                                                              25.0                                                                              18.1                                                                              22.3                  Malonate                                                                              (1,2)          propylamine (1,3)                                                                      ether                                       6 β -Propiolac-                                                                    Diethylenetriamine                                                                        0.92                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.14                                                                              22.2                                                                               2.8                                                                               4.3                  tone 2                 propylamine (1,3)                                                                      ether                                       7 Succinic Acid                                                                         Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.14                                                                              28.0                                                                              15.1                                                                              17.0                          (1,2)          propylamine (1,3)                                                                      ether                                       8 Succinic                                                                              Diethylenetriamine                                                                        0.94                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.14                                                                              22.0                                                                              13.2                                                                              16.5                  Anhydride                                                                             (1,2)          propylamine (1,3)                                                                      ether                                       9 Maleic  Tetraethylenepenta-                                                                       0.94                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.14                                                                              26.0                                                                              10.2                                                                              14.0                  Anhydride                                                                             mine (1,2)     propylamine (1,3)                                                                      ether                                         3                                                                          10 Diethyl Bis(aminopropyl)                                                                          0.75                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.15                                                                              14.0                                                                              15.5                                                                              17.5                  Succinate                                                                             methylamine (1,3)                                                                            propylamine (1,3)                                                                      ether                                      11 Mono-Methyl                                                                           Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.14                                                                              21.7                                                                              15.0                                                                              16.0                  Succinate                                                                             (1,2)          propylamine (1,3)                                                                      ether                                      12 DL-Malic Acid                                                                         Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.14                                                                              25.0                                                                              13.2                                                                              15.5                  4       (1,2)          propylamine (1,3)                                                                      ether                                      13 Succinyl                                                                              Diethylenetriamine                                                                        0.93                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.14                                                                              32.8                                                                               1.8                                                                               1.9                  Chloride                                                                              (1,2)          propylamine (1,3)                                                                      ether                                      14 Fumaric Acid                                                                          Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Methylene                                                                             1   1.09                                                                              16.0                                                                               1.0                                                                               1.0                  3 11    (1,2)          propylamine (1,3)                                                                      dibromide                                  15 Glutaric Acid                                                                         Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Dichloroethyl                                                                         1   1.05                                                                              25.0                                                                              18.6                                                                              21.6                          (1,2)          propylamine (1,3)                                                                      ether                                      16 Glutaric                                                                              Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.05                                                                              25.0                                                                              18.0                                                                              21.8                  Anhydride                                                                             (1,2)          propylamine (1,3)                                                                      ether                                      17 Dimethyl                                                                              Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.31                                                                              60.0                                                                              21.2                                                                              22.6                  Glutarate                                                                             (1,2)          propylamine (1,3)                                                                      ether                                      18 Itaconic Acid                                                                         Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Triglycol                                                                             1   1.14                                                                              18.8                                                                              18.4                                                                              22.8                  3       (1,2)          propylamine (1,3)                                                                      dichloride                                 19 γ-Valerolac-                                                                    Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.14                                                                              33.3                                                                               1.7                                                                               1.8                  tone 2  (1,2)          propylamine (1,3)                                                                      ether                                      20 γ-Valerolac-                                                                    Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   2.28                                                                              40.2                                                                               2.6                                                                               3.1                  tone 2  (1,2)          propylamine                                                                            ether                                      21 Adipic Acid                                                                           Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.14                                                                              10.0                                                                              21.2                                                                              24.1                          (1,2)          propylamine (1,3)                                                                      ether                                      22 Adipic Acid                                                                           Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.34                                                                              41.7                                                                              18.7                                                                              22.9                          (1,2)          propylamine (1,3)                                                                      ether                                      23 Adipic Acid                                                                           Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          2   1.15                                                                              30.0                                                                              19.3                                                                              23.1                          (1,2)          propylamine (1,3)                                                                      ether                                      24 Adipic Acid                                                                           Pentaethylene-                                                                            0.95                                                                             Aminoethyl                                                                             Dichlorethyl                                                                          2   0.91                                                                              29.8                                                                              15.2                                                                              17.5                          hexamine (1,2) ethanolamine(1,2)                                                                      ether                                      25 Adipic Acid                                                                           Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Triglycol                                                                             1   1.14                                                                              34.5                                                                              19.9                                                                              24.4                          (1,2)          propylamine (1,3)                                                                      dichloride                                 26 Adipic Acid                                                                           Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Ethylene                                                                              1   1.14                                                                              34.7                                                                              20.2                                                                              23.8                          (1,2)          propylamine (1,3)                                                                      dibromide                                  27 Adipic Acid                                                                           Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Diiodomethane                                                                         1   1.14                                                                              34.5                                                                              19.6                                                                              24.6                          (1,2)          propylamine (1,3)                                   28 Adipic Acid                                                                           Triethylenetetramine                                                                      0.95                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.02                                                                              28.0                                                                              15.4                                                                              18.1                          (1,2)          propylamine (1,3)                                                                      ether                                      29 Adipic Acid                                                                           Pentaethylenehexamine                                                                     0.95                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.02                                                                              24.0                                                                              15.2                                                                              16.6                          (1,2)          propylamine (1,3)                                                                      ether                                      30 Adipic Acid                                                                           Bis(aminopropyl)-                                                                         0.95                                                                             Dimethylamino-                                                                         Triglycol                                                                             1   1.27                                                                              15.8                                                                              16.4                                                                              20.0                          methylamine (1,3)                                                                            propylamine (1,3)                                                                      dichloride                                 31 Adipic Acid                                                                           Bis(aminopropyl)-                                                                         0.95                                                                             Aminoethyl-                                                                            Dichlorethyl                                                                          1   1.27                                                                              16.5                                                                              14.1                                                                              16.5                          methylamine (1,3)                                                                            ethanolamine(1,2)                                                                      ether                                      32 Adipic Acid                                                                           Diethylenetriamine                                                                        0.95                                                                             Aminoethyl-                                                                            Dichlorethyl                                                                          1   1.05                                                                              19.1                                                                              16.9                                                                              19.5                          (1,2)          ethanolamine(1,2)                                                                      ether                                      33 Adipic Acid                                                                           Triethylenetetramine                                                                      0.95                                                                             Aminoethyl-                                                                            Dichlorethyl                                                                          1   1.05                                                                              24.0                                                                              13.9                                                                              16.7                          (1,2)          ethanolamine(1,2)                                                                      ether                                      34 Adipic Acid                                                                           Pentaethylenehexamine                                                                     0.95                                                                             Aminoethyl-                                                                            Dichlorethyl                                                                          1   1.05                                                                              33.3                                                                              14.8                                                                              17.4                          (1,2)          ethanolamine(1,2)                                                                      ether                                      35 Adipic Acid                                                                           Diethylenetriamine                                                                        0.85                                                                             Dimethylamino-                                                                         Triglycol                                                                             1   1.27                                                                              18.0                                                                              21.0                                                                              24.7                          (1,2)          propylamine (1,3)                                                                      dichloride                                 36 Adipic Acid                                                                           Diethylenetriamine                                                                        0.9                                                                              Dimethylamino-                                                                         Triglycol                                                                             1   1.20                                                                              18.0                                                                              21.4                                                                              23.6                          (1,2)          propylamine (1,3)                                                                      dichloride                                 37 Adipic Acid                                                                           Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   0.84                                                                              23.4                                                                              18.0                                                                              21.5                          (1,2)          propylamine (1,3)                                                                      ether                                      38 Adipic Acid                                                                           Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.05                                                                              15.1                                                                              21.0                                                                              23.5                          (1,2)          propylamine (1,3)                                                                      ether                                      39 Adipic Acid                                                                           Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.57                                                                              16.4                                                                              20.1                                                                              23.4                          (1,2)          propylamine (1,3)                                                                      ether                                      40 Adipic Acid                                                                           Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.89                                                                              34.7                                                                              15.0                                                                              18.1                          (1,2)          propylamine (1,3)                                                                      ether                                      41 Adipic Acid                                                                           Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.34                                                                              41.7                                                                              22.3                                                                              27.2                          (1,2)          propylamine (1,3)                                                                      ether               6   6                  42 Monomethyl                                                                            Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.14                                                                              18.5                                                                              19.2                                                                              22.8                  Adipate (1,2)          propylamine (1,3)                                                                      ether                                      43 Citric Acid                                                                           Diethylenetriamine                                                                        0.90                                                                             Dimethylamino-                                                                         Triglycol                                                                             1   1.14                                                                              22.0                                                                               7.0                                                                              10.4                  7       (1,2)          propylamine (1,3)                                                                      dichloride                                 44 Adipic Acid                                                                           Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.14                                                                              10.0                                                                              25.8                                                                              30.2                          (1,2)          propylamine (1,3)                                                                      ether               8   9                  45 Pimelic Acid                                                                          Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.05                                                                              14.5                                                                              16.1                                                                              19.9                          (1,2)          propylamine (1,3)                                                                      ether                                      46 Suberic Acid                                                                          Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.14                                                                              11.0                                                                              18.0                                                                              21.8                          (1,2)          propylamine (1,3)                                                                      ether                                      47 Azelaic Acid                                                                          Tetraethylene-                                                                            0.95                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   0.70                                                                              20.0                                                                              14.1                                                                              17.6                          pentamine (1,2)                                                                              propylamine (1,3)                                                                      ether                                      48 Azelaic Acid                                                                          Diethylenetriamine                                                                        0.95                                                                             Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.0 24.0                                                                              19.9                                                                              24.0                          (1,2)          propylamine (1,3)                                                                      ether                                      49 Sebacic Acid                                                                          Diethylenetriamine                                                                        0.9                                                                              Dimethylamino-                                                                         Dichlorethyl                                                                          1   1.14                                                                              20.0                                                                              14.5                                                                              15.4                          (1,2)          propylamine (1,3)                                                                      ether                                      __________________________________________________________________________     1 = Epichlorohydrin                                                           2 = Epibromohydrin                                                       

                                      TABLE Ia                                    __________________________________________________________________________    Base Polyamide   Terminated Base                                                                         Extended Base                                                                           Resin (Epoxidation)                      Example                                                                            Actual                                                                              Temp. Actual                                                                            Temp. Actual                                                                            Temp. Actual                                                                             Temp.                               No.  Temp. Range Temp.                                                                             Range Temp.                                                                             Range Temp.                                                                              Range                               __________________________________________________________________________     1    22    5-25  80 70-90  80 70-90 75   40-70                                2   160   120-160                                                                             150 120-160                                                                             100 100-120                                                                             75-85                                                                              40-90                                3   200   120-200                                                                             165 120-180                                                                             100 100-120                                                                             70-75                                                                              40-90                                4   200   120-240                                                                             165 120-180                                                                             100 100-120                                                                             70-90                                                                              40-90                                5    84-144                                                                              80-160                                                                              85  80-100                                                                              85  80-100                                                                             65   40-90                                6   120   100-150                                                                             120 100-150                                                                             110 100-120                                                                             75-85                                                                              40-90                                7   200   120-240                                                                             165 120-180                                                                             105 110-120                                                                             70-76                                                                              40-90                                8   202   120-240                                                                             180 120-180                                                                             107 100-120                                                                             70-86                                                                              40-90                                9   200   120-240                                                                             180 120-180                                                                             105 100-120                                                                             65-80                                                                              40-90                               10   200    80-200                                                                             100  80-160                                                                             108  80-110                                                                             75-80                                                                              40-90                               11   200   120-240                                                                             160 120-180                                                                             105 100-120                                                                             75   40-90                               12   150   120-155                                                                             120 100-120                                                                             102 100-120                                                                             65   40-90                               13   10-15  0-25  25 20-30 100 100-120                                                                             70   40-90                               14   160   120-170                                                                             130 120-160                                                                             100 100-120                                                                             80   40-90                               15   174   120-175                                                                             170 120-170                                                                             101 100-120                                                                             57   40-90                               16   162   120-165                                                                             170 120-170                                                                             102 100-120                                                                             54   40-90                               17    80-150                                                                              80-170                                                                              90  80-100                                                                              80  80-100                                                                             50   40-90                               18   200   120-240                                                                             170 120-180                                                                             103 100-120                                                                             75   40-90                               19   240   120-240                                                                             150 120-180                                                                             110 100-120                                                                             75   40-90                               20   240   120-240                                                                             150 120-180                                                                             110 100-120                                                                             75   40-90                               21   200   120-240                                                                             165 120-180                                                                             105 100-120                                                                             75   40-90                               22   200   120-240                                                                             165 120-180                                                                             105 100-120                                                                             75   40-90                               23   210   120-240                                                                             180 120-180                                                                             106 100-120                                                                             60- 65                                                                             40-90                               24   200   120-240                                                                             165 120-180                                                                             114 100-120                                                                             60-68                                                                              40-90                               25   210   120-240                                                                             168 120-180                                                                             100 100-120                                                                             60-63                                                                              40-90                               26   210   120-240                                                                             168 120-180                                                                             101 100-120                                                                             60-64                                                                              40-90                               27   210   120-240                                                                             168 120-180                                                                             100 100-120                                                                             60   40-90                               28   210   120-240                                                                             165 120-180                                                                             107 100-120                                                                             63-70                                                                              40-90                               29   200   120-240                                                                             165 120-180                                                                             118 100-120                                                                             62-72                                                                              40-90                               30   200   120-240                                                                             175 120-180                                                                             105 100-120                                                                             70   40-90                               31   200   120-240                                                                             170 120-180                                                                             105 100-120                                                                             70   40-90                               32   200   120-240                                                                             165 120-180                                                                             109 100-120                                                                             62-75                                                                              40-90                               33   200   120-240                                                                             165 120-180                                                                             110 100-120                                                                             60-75                                                                              40-90                               34   200   120-240                                                                             165 120-180                                                                             114 100-120                                                                             70-72                                                                              40-90                               35   200   120-240                                                                             154 120-180                                                                             107 100-120                                                                             70-75                                                                              40-90                               36   200   120-240                                                                             160 120-180                                                                             105 100-120                                                                             70-73                                                                              40-90                               37   210   120-240                                                                             180 120-180                                                                             106 100-120                                                                             60-68                                                                              40-90                               38   200   120-240                                                                             165 120-180                                                                             106 100-120                                                                             70-72                                                                              40-90                               39   200   120-240                                                                             165 120-180                                                                             106 100-120                                                                             70-85                                                                              40-90                               40   210   120-240                                                                             180 120-180                                                                             106 100-120                                                                             70-75                                                                              40-90                               41   200   120-240                                                                             165 120-180                                                                             105 100-120                                                                             50   40-90                               42   201   120-240                                                                             175 120-180                                                                             106 100-120                                                                             60-75                                                                              40-90                               43   200   120-240                                                                             150 120-180                                                                             105 100-120                                                                             73   40-90                               44   200   120-240                                                                             165 120-180                                                                             105 100-120                                                                             70   40-90                               45   200   120-240                                                                             177 120-180                                                                             104 100-120                                                                             70-80                                                                              40-90                               46   200   120-240                                                                             170 120-180                                                                             103 100-120                                                                             57   40-90                               47   202   120-240                                                                             175 120-180                                                                             103 100-120                                                                             45   40-90                               48   200   120-240                                                                             167 120-180                                                                             100 100-120                                                                             51   40-90                               49   180   120-240                                                                             155 120-180                                                                             105 100-120                                                                             65   40-90                               __________________________________________________________________________

                                      TABLE Ib (wt. in grams; time in             __________________________________________________________________________    hours)                                                                        Base Polyamide        Terminated Base                                                                           Extended Base                                                                              Epoxidized                     Ex.     II. Backbone                                                                             Rx.                                                                              III. Terminating                                                                      Rx. IV. Chain                                                                              Rx. V. Epoxidizing                                                                            Rx.                No.                                                                              I. Acid                                                                            Polyamine                                                                            Water                                                                             Time                                                                             Polyamine                                                                             Time                                                                              Extender                                                                           Water                                                                             Time                                                                              Agent   Water                                                                             Time               __________________________________________________________________________     1 25   22.5    30 12                                                                            20°                                                                       4.1     1°30'                                                                      2.5   40 2°                                                                         36       0  3°           2 42   32.5    84 2°                                                                        3.3     1°                                                                         2.3   20 1°                                                                         34      128 4°15'        3 104  97.8   104 2°8'                                                                      10.2    1°                                                                         10.0 100 1°30'                                                                      100     800 13°          4 52   80.0    52 2°55'                                                                     5.1     1°                                                                         5.0   75 1°30'                                                                      110     500 13°          5 160  97.0    0  4°45'                                                                     11.0    1°                                                                         8.0  100 1°16'                                                                      100     600 4°50'        6 72   95.0    0  2°                                                                        18.0    1°                                                                         12.0 100 1°30'                                                                      100     900 14°30'       7 118  97.8   118 2°15'                                                                     10.2    1°                                                                         8.0  100 1°30'                                                                      100     700 7°25'        8 51   48.5    51 1°                                                                        6.0     1°25'                                                                      4.0   50 1°30'                                                                      500      60 7°37'        9 49   89.0   100 1°40'                                                                     10.0    1°40'                                                                      5.0   70 1°35'                                                                      70      700 6°35'       10 87   54.4    0  3°                                                                        25.5    1°                                                                         18.0  50 2°                                                                         50      455 8°30'       11 66   49.0    66 1°30'                                                                     5.1     1°                                                                         4.0   50 1°                                                                         50      500 9°20'       12 134  97.8   134 3°                                                                        10.2    1°                                                                         8.0  100 1°30'                                                                      100     600 7°40'       13 77.5 48.0   200 13                                                                            1°45'                                                                     5.0     30' 4.0  100 1°                                                                         50      200 13°30'      14 58   49.0   100 2°                                                                        5.1     15' 6.0  100 2°                                                                         48      270 3°30'       15 66   49.0    66 2°30'                                                                     5.1     55' 4.0  150 1°20'                                                                      46.2    276 1°16'       16 57   49.0    57 2°15'                                                                     5.1     1°14'                                                                      4.0   50 1°35'                                                                      46.2    350 1°26'       17 384  234.8   0  1°8'                                                                      24.5    55' 18.0 300 1°22'                                                                      277.0    0  2°23'       18 65   48.9    65 1°30'                                                                     5.1     1°10'                                                                      5.0  100 1°30'                                                                      50.0    550 5°          19 50   49.0    0  3°                                                                        5.1     1°                                                                         4.0   50 1°30'                                                                      50.0    250 7°30'       20 50   49.0    0  3°                                                                        5.1     1°                                                                         4.0   50 1°30'                                                                      100.0   250 7°30'       21 292  195.7  292 3°10'                                                                     25.0    2°                                                                         16.0 200 1°30'                                                                      200.0   2400                                                                              3°45'       22 292  195.7  292 4°30'                                                                     25.0    2°                                                                         16.0 200 1°30'                                                                      237.0   195 5°50'       23 146  97.8   146 2°                                                                        12.5    2°                                                                         8.0  100 1°30'                                                                      150.0   400 1°35'       24 146  220.0  146 2°                                                                        10.4    1°                                                                         8.0  100 1°30'                                                                      120.0   1200                                                                              1°20'       25 146  97.8   146 2°45'                                                                     12.5    2°                                                                         10.5 480 2°30'                                                                      99.0     0  1°50'       26 146  97.8   146 2°45'                                                                     12.5    2°                                                                         10.5 480 2°30'                                                                      99.0     0  2°10'       27 146  97.8   146 2°45'                                                                     12.5    2°                                                                         13.5 480 2°30'                                                                      99.0     0  1°45'       28 146  138.7  146 1°30'                                                                     10.2    1°15'                                                                      8.0  125 1°30'                                                                      180.0   930 6°40'       29 146  220.0  146 1°30'                                                                     10.2    1°10'                                                                      8.0   75 1°30'                                                                      360.0   1940                                                                              7°50'       30 146  136.0  146 1°30'                                                                     10.2    1°10'                                                                      10.0 100 1°30'                                                                      112.0   1000                                                                              1°15'       31 146  136.0  146 1°30'                                                                     10.4    1°10'                                                                      8    100 1°30'                                                                      112.0   1000                                                                              6°          32 146  97.8   146 1°30'                                                                     10.4    1°20'                                                                      8    100 1°30'                                                                      92.0    800 13°30'      33 146  138.7  146 1°30'                                                                     10.4    1°15'                                                                      8    100 1°30'                                                                      184.0   1280                                                                              13°45'      34 146  220.0  146 1°30'                                                                     10.4    1°15'                                                                      8    100 1°30'                                                                      368.0   1200                                                                              7°30'       35 146  87.5   146 1°                                                                        30.6    1°15'                                                                      10   100 1°30'                                                                      100.0   800 55'                36 146  92.7   146 1°                                                                        20.4    1°10'                                                                      10   100 1°30'                                                                      100.0   800 1°50'       37 146  97.8   146 2°                                                                        12.5    2°                                                                         8    100 1°30'                                                                      74.0    400 2°10'       38 146  97.8   146 3°10'                                                                     12.5    2°                                                                         8    100 1°30'                                                                      92.4    1150                                                                              1°15'       39 146  97.8   146 3°10'                                                                     12.5    2°                                                                         8    100 1°30'                                                                      138.0   1150                                                                              14°         40 146  97.8   146 2°                                                                        12.5    2°                                                                         8    100 1°30'                                                                      166.8   400 15°         41 292  195.7  292 4°30'                                                                     25.0    2°                                                                         16   200 1°30'                                                                      237.0   195 5°50'       42 32   19.6    0  1°15'                                                                     2.5     2°45'                                                                      1.5   20 1°30'                                                                      20.0    125 6°10'       43 105  70.0    96 1°                                                                        10.2    1°                                                                         5    100 1°30'                                                                      100.0   900 5°30'       44 292  195.7  292 3°10'                                                                     25.0    2°                                                                         16   200 1°30'                                                                      200.0   2400                                                                              3°45'       45 40   24.4    40 1°45'                                                                     3.0     1°35'                                                                      2.5   30 1°37'                                                                      23.2    445 7°10'       46 87   48.9    87 2°10'                                                                     5.1     1°25'                                                                      4     50 1°36'                                                                      50.0    260 2°15'       47 94   90.0    94 2°45'                                                                     5.1     15' 4    100 1°                                                                         92.5    800 21'                48 94   48.9    94 1°20'                                                                     5.1     1°15'                                                                      4     50 1°30'                                                                      46.2    366 2°15'       49 101  46.6    96 2°50'                                                                     10.2    1°15'                                                                      8     50 1°30'                                                                      50.0    300 4°35'       __________________________________________________________________________

TABLES II, IIa, AND IIb

The following tables contain summaries of the preparation and wetstrength test results of nineteen resins which are not within the scopeof this invention. The resins were prepared according to the U.S. Pat.Nos. 2,926,116 and 2,926,154, unless otherwise indicated. Table IIindicates the reactants, their mole ratios, and the activity and % wetstrength of the resins. Table IIa gives the actual temperatures used inthe synthesis as well as the range disclosed by the art upon which theexample was based. Table IIb gives the reactant quantities and the timesof the reactant steps. A key to the footnotes in Tables II and IIb willbe found at the end of Table IIb.

                                      TABLE II                                    __________________________________________________________________________                                                  Mole                                      II. Backbone                                                                             Mole                                                                             III. Terminating                                                                       IV.          Ratio    % Wet Strength         Ex.       Polyamine  Ratio                                                                            Polyamine                                                                              Chain                                                                              V. Epoxidizing                                                                        V/active                                                                           %   0.5%                                                                              1.0%               No.                                                                              I. Acid                                                                              (prim, sec, tert)                                                                        II/I                                                                             (prim, sec, tert)                                                                      Extender                                                                           Agent   NH   Active                                                                            added                                                                             added              __________________________________________________________________________    50 Sebacic Acid                                                                         Diethylenetriamine                                                                       0.95                                                                             Dimethylamino-                                                                         Dichlor-              water                             (1,2)        propylamine(1,3)                                                                       ethyl                 insoluble              51 Diethyl                                                                              Diethylenetriamine                                                                       1.0         ether                                                                              Epichlorohydrin                                                                       1.2  42.2                                                                               6.1                                                                               9.0                  Oxalate 1                                                                             (1,2)                                                              52 Diethyl                                                                              Triethylenetetramine                                                                     1.0              Epichlorohydrin                                                                       1.2   8.5                                                                              11.1                                                                              13.7                  Oxalate 1                                                                             (1,2)                                                              53 Oxalic Acid 1                                                                        Diethylenetriamine                                                                       1.09             Epichlorohydrin                                                                       1.08 20.3                                                                               1.3                                                                               1.7                          (1,2)                                                              54 Malonic Acid                                                                         Diethylenetriamine                                                                       1.09             Epichlorohydrin                                                                       1.08 19.8                                                                               1.4                                                                               1.5                          (1,2)                                                              55 Succinic Acid                                                                        Diethylenetriamine                                                                       1.06             Epichlorohydrin                                                                       1.0  21.5                                                                              13.9                                                                              20.0                          (1,2)                                                              56 Glutaric Acid                                                                        Diethylenetriamine                                                                       1.08             Epichlorohydrin                                                                       1.08 17.4                                                                              16.0                                                                              20.0                          (1,2)                                                              57 Dimethyl                                                                             Diethylenetriamine                                                                       1.1              Epichlorohydrin                                                                       1.0  15.0                                                                              15.5                                                                              16.5                  Glutarate 1                                                                           (1,2)                                                              58 Itaconic Acid                                                                        Diethylenetriamine                                                                       1.1              Epichlorohydrin                                                                       1.0  10.0                                                                              17.0                                                                              21.0                  3 5     (1,2)                                                              59 Adipic Acid                                                                          Diethylenetriamine                                                                       1.1              Epichlorohydrin                                                                       1.0  10.0                                                                              18.5                                                                              22.0                          (1,2)                                                              60 Adipic Acid                                                                          Diethylenetriamine                                                                       1.1              Epichlorohydrin                                                                       1.0  10.0                                                                              24.8                                                                              28.3                          (1,2)                                       8   9                  61 Adipic Acid                                                                          Diethylenetriamine                                                                       0.95                                                                             Dimethylamino-                                                                         Dichlor-                                                                           Ethylene                                           (1,2)        propylamine(1,3)                                                                       ethyl                                                                              dibromide 10                                                                          1.39 14.0                                                                               5.5                                                                               7.4               62 Pimelic Acid                                                                         Diethylenetriamine                                                                       1.10        ether                                                                              Epichlorohydrin                                                                       1.0  11.0                                                                              gel --                            (1,2)                                                              63 Suberic Acid                                                                         Diethylenetriamine                                                                       1.10             Epichlorohydrin                                                                       1.0      gel --                            (1,2)                                                              64 Suberic Acid                                                                         Diethylenetriamine                                                                       1.4              Epichlorohydrin                                                                       0.5   8.0                                                                               3.7                                                                               5.1                         + Ethylenediamine                                                             Ratio 2/3                                                           65 Suberic Acid                                                                         Ethylenediamine                                                                          1.1              Epichlorohydrin                                                                       1.0      gel --                           + Diethylenetriamine                                                          Ratio 1:10                                                          66 Suberic Acid                                                                         Ethylenediamine                                                                          1.1              Epichlorohydrin                                                                       0.5      gel --                           + Diethylenetriamine                                                          Ratio 1:10                                                          67 Suberic Acid                                                                         Ethylenediamine                                                                          1.1              Epichlorohydrin                                                                       0.5      gel --                           + Diethylenetriamine                                                          Ratio 4:6                                                           68 Suberic Acid                                                                         Ethylenediamine                                                                          1.1              Epichlorohydrin                                                                       1.0      gel --                           + Diethylenetriamine                                                          Ratio 4:6                                                           __________________________________________________________________________

                                      TABLE IIa                                   __________________________________________________________________________    Base Polyamide Terminated Base                                                                        Extended Base                                                                          Resin (Epoxidation)                          Example                                                                            Actual                                                                             Temp.                                                                              Actual                                                                            Temp.                                                                              Actual                                                                            Temp.                                                                              Actual                                                                             Temp.                                   No.  Temp.                                                                              Range                                                                              Temp.                                                                             Range                                                                              Temp.                                                                             Range                                                                              Temp.                                                                              Range                                   __________________________________________________________________________    50   180  120-240                                                                            155 120-180                                                                            105 100-120                                                                            --   --                                      51    22  15-25                  60-70                                                                              50-80                                   52    22  15-25                  60-70                                                                              50-80                                   53   150  120-160                75-85                                                                              45-100                                  54   185  110-250                75-85                                                                              45-100                                  55   200  110-250                66-68                                                                              45-100                                  56   185  110-250                70   45-100                                  57   150  110-250                75   45-100                                  58   165  160-210                85   60-100                                  59   185-200                                                                            110-250                60-70                                                                              45-100                                  60   185-200                                                                            110-250                60-70                                                                              45-100                                  61   200  120-240                                                                            165 120-180                                                                            105 100-120                                                                            94   50-100                                  62   195  110-250                65   45-100                                  63   194  110-250                56   45-100                                  64   198  110-250                76   45-100                                  65   185-200                                                                            110-250                60-65                                                                              45-100                                  66   185-200                                                                            110-250                45   45-100                                  67   185-200                                                                            110-250                50   45-100                                  68   185-200                                                                            110-250                45   45-100                                  __________________________________________________________________________

                                      TABLE IIb (wt. in grams; time in            __________________________________________________________________________    hours)                                                                        Base Polyamide        Terminated Base                                                                           Extended Base                                                                              Epoxidized                     Ex.    II. Backbone                                                                             Rx. III. Terminating                                                                      Rx. IV. Chain                                                                              Rx. V. Epoxidizing                                                                            Rx.                No.                                                                              I. Acid                                                                           Polyamine                                                                            Water                                                                             Time                                                                              Polyamine                                                                             Time                                                                              Extender                                                                           Water                                                                             Time                                                                              Agent   Water                                                                             Time               __________________________________________________________________________    50 101 48.9   101 1°30'                                                                      5.1     1°45'                                                                      4    50  1°40'                       51 40  28.3   160 12                                                                            20°                   30.5    200 2°          52 40  40.0   160 12                                                                            20°                   61.0    200 3°          53 63  56.0    60 1°                    50.0    500 8°          54 52  56.0    50 2°                    50.0    400 3°50'       55 118 109.0  100 1°30'                 92.0    1000                                                                              45'                56 66  56.0    50 1°30'                 50.0    520 30'                57 160 113.0   0  2°                    92.5    1660                                                                              3°          58 65  56.0    50 3°                    50.0    450 4°          59 292 226.6  100 2°                    185.0   3800                                                                              8°          60 292 226.6  100 2°                    185.0   3800                                                                              8°          61 146 97.8   146 2°                                                                         12.5    2°                                                                         8    100 1°30'                                                                      250.0   1800                                                                              3°          62 40  28.4    20 3°                    23.2    470 1°10'       63 87  56.3    25 3°35'                 46.4    450 38'                64 87  28.8 + 25.2                                                                           25 1°50'                 13.0    920 5°40'       65 87  8   + 51.5                                                                            25 1°50'                 46.3    940 16'                66 87  3   + 51.5                                                                            25 1°50'                 23.1    940 40'                67 87  13.2 + 34                                                                             25 1°50'                 13.9    940 16'                68 87  13.2 + 34                                                                             25 1°50'                 27.8    940 37'                __________________________________________________________________________     Footnotes to Tables I, Ib and II, IIb                                         1 outside the scope of U.S. 2,926,116 and 2,926,154, but prepared             according to their method.                                                    2 considered to be a mono-acid.                                               3 unsaturated acid                                                            4 hydroxy acid.                                                               5 prepared according to U.S. Patent No. 3,125,552.                            6 results after 19 days of aging.                                             7 tri-acid.                                                                   8 2.0% concentration instead of 0.5%.                                         9 3.0% concentration instead of 1.0%.                                         10 a chain extender (quaternizing agent) was used instead of an               epoxidizing agent                                                             11 decarboxylates.                                                            12 isopropanol was used in place of the water.                                13 benzene was used in place of the water.                               

7. INTERPRETATION OF TABLES I, Ia, Ib, and II, IIa, IIb A. Tables I, Ia,Ib

Examples Nos. 1 through 49 disclose various reactants, most of which arerepresentative of those useful in this invention, as well asrepresentative reaction conditions.

Examples 1 - 21, and 42 - 49 disclose different acids. Most of theseexamples use the identical backbone polyamine, terminating polyamine,chain extender, and epoxidizing agent, so as to afford an objectivebasis for analyzing the relative merits of the acids.

It is thus apparent that Examples 2, 3, 4, 6, 13, 14, 19, and 20 useacids that are not suitable for making the wet strength resins of thisinvention. Particularly interesting is the fact that the saturated acidsof Examples 2, 3, and 4 decarboxylate and are therefore unsuitable,whereas their corresponding esters (Examples 1 and 5) are excellent.Example 13 shows that acyl halides are unsuitable, Examples 19 and 20show that lactones and unsuitable, and Example 14 shows that thoseunsaturated acids which decarboxylate are unsuitable.

Useful saturated dicarboxylic acids are disclosed in Examples 7, 12, 15,18, 21-41, and 43-49. A useful unsaturated dicarboxylic acid isdisclosed in Example 18. A useful tricarboxylic acid is disclosed inExample 43. Useful C₁₋₁₂ alkyl mono- and di-esters are disclosed inExamples 1, 5, 10, 11, 17, and 42. Useful anhydrides are disclosed inExamples 8, 9, and 16.

Various backbone polyamines, terminating polyamines, chain extenders,and epoxidizing agents are also disclosed in the examples with the scopeof this invention.

The mole ratios of backbone polyamine to acid of examples within thescope of this invention in Table I vary from 0.75 to 0.95. This moleratio was purposely kept at about 0.95 very frequently in order tocompare the efficacy of the reactants on an objective basis. The moleratios of epoxidizing agent to active amino groups of Examples in TableI within the scope of this invention vary from 0.70 to 1.89.

Particular attention should be given to Examples 21-41. These all useadipic acid and disclose that great variation of the other reactants andof the mole ratios are possible.

The "% Active" column is extremely important for reasons notedpreviously under "Reactant Parameters." It must be understood, ofcourse, that the activity of a resin is secondary to its "% WetStrength." If a resin has a low wet strength, its activity is completelyirrelevant to tits usefulness.

B. TABLES II, IIa, IIb

Examples 50 through 68 disclose resins outside the scope of thisinvention.

Example 50 was made with reactant ingredients that are within the scopeof this invention, but with a mole ratio of backbone polyamine to acidthat was too high (0.95), resulting in a water insoluble polyamide thatcould not be epoxidized. Example 49 used the same reactants, but with alower mole ratio (0.9). This indicates that the mole ratio of backbonepolyamine to acid should be within the lower part of the mole ratiorange when a higher acid is used.

Example 61 differs from those within the scope of this invention only inthat an expoxidizing agent outside the scope of the invention was used.It should be noted that the epoxidizing agent is useful as a chainextender in this invention, and is well known as a quaternizing agent.This shows that the chain extension and epoxidation steps of thisinvention are distinct, and that the reactants are not interchangeable.

Examples 54-56, 59, 60, and 62-68 are within the scope of U.S. Pat. Nos.2,926,116 or 2,926,154. It is noted that only Examples 55, 56, and 59and 60 would be wet strength resins according to the accepted definition(see "Testing of Wet Strength Efficiency," supra), and that the highest% Activity among them is 21.5.

Particular attention should be given to Examples 63-68, all of whichused the same reactants. Various mole ratios, temperatures, andreactants were tried, all being within the scope of the above patents,but a wet strength resin could not be produced.

Examples 51-53, and 57 are outside the scope of the above patentsbecause of the choice of acid or substituted acid. It should be notedthat Examples 51 and 52 differ only as to the choice of backbonepolyamine, and that Example 52 shows wet strength properties, althoughof a poor caliber.

Example 58 is within the scope of the U.S. Pat. No. 3,125,552. This is awet strength resin as defined herein, although the % Activity is only10.

8. USE OF RESINS AT VARIOUS PULP pH VALUES

The wet strength resins of this invention may be used under both acidand alkaline pulp conditions. The following table shows that two batchesof a typical resin (that of Example 22) were both effective for wetstrength purposes when used with pulp pH values of from 4 to 10.

                  Table III                                                       ______________________________________                                                % Wet Strength                                                        Pulp pH   0.5% added   1.0% added   Batch                                     ______________________________________                                        4.0       18.7         22.4         1                                         5.0       16.2         20.0         2                                         6.0       20.3         22.2         2                                         7.0       21.0         26.5         *                                         8.0       21.4         29.2         *                                         9.0       21.2         27.4         2                                         10.0      22.1         29.1         1                                         ______________________________________                                         *average of tests on two batches                                         

9. AGEING AND STABILITY QUALITIES

Samples of resins both within and outside the scope of this inventionwere tested for stability and efficacy upon ageing. The results were asfollows.

                                      Table IV                                    __________________________________________________________________________                           Original                                                                              Aged    % of Wet                               Resin of          Temper-                                                                            Wet Strength                                                                          Wet Strength                                                                          Strength Retention                     Sample                                                                            Example No.                                                                           Time  ature                                                                              0.5%                                                                              1.0%                                                                              0.5%                                                                              1.0%                                                                              0.5% 1.0% average                      __________________________________________________________________________    A.  21      349 days                                                                            22° C                                                                       21.8                                                                              23.8                                                                              19.6                                                                              24.6                                                                              90.0 103.0                                                                              96.5                         B.  *       182 days                                                                            22° C                                                                       18.5                                                                              22.0                                                                              16.5                                                                              18.1                                                                              90.0 82.4 86.2                         C.  21       14 days                                                                            50° C                                                                       19.6                                                                              24.6                                                                              1.5 21.0                                                                              94.4 85.3 89.9                         D.  *        9 days                                                                             50° C                                                                       17.3                                                                              21.2                                                                              15.4                                                                              18.8                                                                              89.0 88.6 88.8                         E.  22, 41   19 days                                                                            22° C                                                                       16.2                                                                              20.7                                                                              22.3                                                                              27.2                                                                              137.0                                                                              131.0                                                                              134.0                        F.  22      137 days                                                                            22° C                                                                       19.9                                                                              22.8                                                                              18.8                                                                              22.2                                                                              94.5 97.3 95.9                         __________________________________________________________________________     *The resin of Example I of United States Patents Nos. 2,926,116 and           2,926,154.                                                               

The viscosities of the resin of Example 22 after varying ageing periodswere correlated with their respective wet strengths, in order to providea means for quickly estimating the efficacy of a given resin without thenecessity of preparing handsheets. This data is as follows.

                                      Table V                                     __________________________________________________________________________                      % of Original % of Original                                 Ageing Period                                                                          % Wet Strength                                                                         Wet Strength  Viscosity                                     (50° C)                                                                         (0.5%)   Retained                                                                              Viscosity*                                                                          Retained                                      __________________________________________________________________________    0        22.8     --      620   --                                            3 days   20.5     90      500   81                                            5 days   19.4     85      440   71                                            7 days   17.5     77      405   65                                            9 days   16.2     71      266   43                                            __________________________________________________________________________     *measured in centipoises on a Brookfield Viscometer at 25° C      

Based on a correlation of the figures of Table V, an ageing test wasconducted on additional resins within the scope of this invention, overa 72 period at 50° C. The results were as follows.

                                      Table VI                                    __________________________________________________________________________                                    Estimated % of                                                        % of Original                                                                         Original                                          Resin of                                                                              Initial                                                                             Final Viscosity                                                                             Wet Strength                                  Sample                                                                            Example No.                                                                           Viscosity*                                                                          Viscosity*                                                                          Retained                                                                              Retained                                      __________________________________________________________________________    A.   1      70    50    71      85                                            B.   5      10    10    100     100                                           C.   7      16    15    94      97                                            D.  17      2,700 2,000 74      87                                            E.  34      30    36    120     100+                                          F.  45       5     5    100     100                                           G.  48      85    65    76      88                                            H.  49      12    10    83      91                                            __________________________________________________________________________     *measured in centipoises on a Brookfield Viscometer at 25° C      

10. WASTE PAPER RECYCLING AND BROKE RECOVERY

Most wet strength resins increase the difficulty of recycling wastepaper and recovering broke. Broke is defined as paper that has beendiscarded during the process of its manufacture, and includes webselvage, roll ends, blemished paper, etc. As broke generally constitutesabout 10% of production, its recovery is important. The recovery(repulping) of wet strength treated paper is made difficult by thepresence of the resins, which do not easily degrade. It therefore isadvantageous to use a resin which can degrade during broke recoverywithout a sacrifice of wet strength.

Broke from paper which is treated with the wet strength resins of thisinvention is more easily recovered (i.e.: repulped) than broke frompaper treated with other wet strength resins such as, for example, thoseof U.S. Pat. Nos. 2,926,116 and 2,926,154. In a mill trial, it was foundthat paper containing the resin of Example 22 added at 0.5 to 0.6% and40 percent activity was easily repulped in a hydra pulper at atemperature of 21°-32° C. It is believed that this is primarily due tothe slower polymerization rate of the resins of this invention isrepulped, the resins are still incompletely polymerized and thereforedegrade more easily. The polymerization of the resin is completed uponmoderate aging, and is thus complete by the time the paper is used. Bycontrast, polymerization of the resins of the abovementioned patents iscomplete once the web is produced. The presence of resin-treated paperthat does not degrade can jam the machinery, causing a work stoppagewhile it is physically removed. Small pieces of such paper can blemishthe finished paper.

Another factor contributing to easier broke recovery when using theresins of this invention, is that they have a lesser degree ofself-sizing. That is, the resins of this invention impart a lower degreeof water repellency to the paper than do those of U.S. Pat. Nos.2,926,116 and 2,926,154. As a result, the broke has greater waterabsorbancy and is more easily repulped. Additionally, this propertyeliminates, in part, the need for adding a rewetting agent to the pulpto increase water absorbancy where desired, such as in paper towelling.

Waste paper may also be more easily recovered if it contains the wetstrength resins of this invention. Even when fully polymerized, theresins of this invention are more easily degraded in the repulpingprocess than the resins of the prior art. Melamine-type wet strengthresins, for example, if used in amounts of 1 to 3 percent, cannot bebroken up in the waste paper repulping process. Paper treated with suchresins must be physically removed, and cannot be recycled. The lowerself-sizing properties of paper treated witih the wet strength resins ofthis invention also contributes towards the ease of repulping.

I claim:
 1. A method of manufacturing paper having increased wetstrength comprising adding from about 0.1 to about 5.0 parts by weightof at least one wet strength resin per 100 parts by weight of dry pulpto an aqueous suspension of paper stock, said wet strength resin beingin the form of an aqueous resin solution or colloidal suspensioncomprising:I. a mixture of a resin which is the reaction product ofA. amember selected from at least one of the group consisting ofa. saturateddicarboxylic acids having 4 to 12 carbon atoms; b. non-decarboxylatingunsaturated dicarboxylic acids having from 5 to 12 carbon atoms; c.saturated and non-decarboxylating unsaturated tricarboxylic acids having6 to 10 carbon atoms; d. C₁₋₁₂ alkyl mono- and di-esters of saturatedand unsaturated dicarboxylic acids having 2 to 12 carbon atoms; e. C₁₋₁₂alkyl mono- and di-esters of saturated and unsaturated tricarboxylicacids having 6 to 10 carbon atoms; and f. anhydrides of saturated andunsaturated dicarboxylic acids having 4 or 5 carbon atoms; with B. atleast one backbone polyamine, present in about 0.66 to about 0.99 molesper mole of the member, which may be branched or straight chain, andwhich contains at least two primary amino groups and at least onesecondary or tertiary amino group, with the proviso that if the memberhas 10 or more carbon atoms, not more than 0.90 moles of the backbonepolyamine are present, to form a base polyamide having free carboxylicgroups; C. at least one terminating polyamine, present in an amount atleast sufficient to cap all free carboxylic groups remaining on the basepolyamide, which may be branched or straight chain, and which containsonly one primary amino group and at least one secondary or tertiaryamino group, to form a terminated base; D. a chain extender, present inabout equimolar quantities with the terminated base, selected from atleast one of the group consisting of alkyldihalide, alkyletherdihalide,phenyl bis-(alkylhalide), and phenylalkyldihalide all containing fromone to twelve carbon atoms to form an extended base; and E. anepoxidizing agent, present in about 0.6 to about 1.5 moles per unreactedsecondary or tertiary amino group remaining on the extended base, withthe proviso that the amount of epoxidizing agent is not sufficiently inexcess to reduce the pH of the reaction medium below about 5.0, selectedfrom at least one of the group consisting of epihalohydrins and alkylsubstituted epihalohydrins, with Ii. water, said resin being present inan amount of 70 parts by weight and said water being present in anamount of at least 30 parts by weight.
 2. The method of claim 1 in whichsaid member is selected from at least one of the group consisting of:saturated dicarboxylic acids having 4 to 10 carbon atoms; C₁₋₁₂ alkylmono- and d-esters of saturated and unsaturated dicarboxylic acidshaving 2 to 10 carbon atoms, and anhydrides of saturated and unsaturateddicarboxylic acids having 4 or 5 carbon atoms.
 3. The method of claim 1in which said member is selected from at least one of the groupconsisting of: diethyloxalate; diethylmalonate; succinic acid; succinicanhydride; diethylsuccinate; monomethylsuccinate; maleic anhydride:D,L-malic acid, diglycollic acid; glutaric acid; glutaric anhydrides;dimethylglutarate; itaconic acid; adipic acid; monomethyl adipate;pimelic acid; suberic acid, azelaic acid; and sebacic acid.
 4. Themethod of claim 3 in which said member is adipic acid.
 5. The method ofclaim 3 in which said member is methyl glutarate.
 6. The method of claim1 in which said backbone polyamine is selected from at least one of thegroup consisting of prim, sec-diethylenetriamine; prim,sec-tetraethylenepentamine; prim, tert-bis(aminopropyl) methylamine;prim, sec-pentaethylenehexamine, and prim, sec-triethylenetetramine. 7.The method of claim 6 in which said backbone polyamine is prim,sec-diethylenetriamine.
 8. The method of claim 1 in which saidterminating polyamie is selected from at least one of the groupconsisting of: prim, tert-dimethylaminopropylamine; and prim,sec-aminoethylethanolamine.
 9. The method of claim 8 in which saidterminating polyamine is prim, tert-dimethylaminopropylamine.
 10. Themethod of claim 1 in which said chain extender is selected from at leastone of the group consisting of: methylenedibromide; ethylenedibromide;methylenediiodide; dichloroethylether; dichloroisopropylether; andtriglycoldichloride.
 11. The method of claim 10 in which said chainextender is dichloroethylether.
 12. The method of claim 1 in which saidepoxidizing agent is an epihalohydrin.
 13. The method of claim 12 inwhich said epoxidizing agent is epichlorohydrin.
 14. The method of claim1 in which said member is adipic acid, the backbone polyamine is prim,sec-diethylenetriamine, the terminating amine is prim,tert-dimethylaminopropylamine, the chain extender is dichlorethyletherand the epoxidizing agent is epichlorohydrin.
 15. The method of claim 1in which said member is methyl glutarate, the backbone polyamine isprim, sec-diethylenetriamine, the terminating amine is prim,tert-dimethylaminopropylamine, the chain extender is dichlorethyletherand the epoxidizing agent is epichlorohydrin.
 16. The method of claim 1in which said backbone polyamine is present in about 0.75 to about 0.95moles.
 17. The method of claim 1 in which said epoxidizing agent ispresent in about 1.0 to about 1.4 moles.
 18. Paper produced by themethod of claim
 1. 19. A method of manufacturing paper having increasedwet strength comprising adding from about 0.1 to about 5.0 parts byweight of at least one wet strength resin per 100 parts by weight of drypulp to preformed paper, said wet strength resin being in the form of anaqueous resin solution or colloidal suspension comprising:I. a mixtureof a resin which is the reaction product ofA. a member selected from atleast one of the group consisting ofa. saturated dicarboxylic acidshaving 4 to 12 carbon atoms; b. non-decarboxylating unsaturateddicarboxylic acids having from 5 to 12 carbon atoms; c. saturated andnon-decarboxylating unsaturated tricarboxylic acids having 6 to 10carbon atoms; d. C₁₋₁₂ alkyl mono- and di-esters of saturated andunsaturated dicarboxylic acids having 2 to 12 carbon atoms; e. C₁₋₁₂alkyl mono- and di-esters of saturated and unsaturated tricarboxylicacids having 6 to 10 carbon atoms; and f. anhydrides of saturated andunsaturated dicarboxylic acids having 4 or 5 carbon atoms; with B. atleast one backbone polyamine, present in about 0.66 to about 0.99 molesper mole of the member, which may be branched or straight chain, andwhich contains at least two primary amino groups and at least onesecondary or tertiary amino group, with the proviso that if the memberhas 10 or more carbon atoms, not more than 0.90 moles of the backbonepolyamine are present, to form a base polyamide having free carboxylicgroups; C. at least one terminating polyamine, present in an amount atleast sufficient to cap all free carboxylic groups remaining on the basepolyamide, which may be branched or straight chain, and which containsonly one primary amino group and at least one secondary or tertiaryamino group, to form a terminated base; D. a chain extender, present inabout equimolar quantities with the terminated base, selected from atleast one of the group consisting of alkyldihalide, alkyletherdihalide,phenyl bis-(alkylhalide), and phenylalkyldihalide, all containing fromone to twelve carbon atoms to form an extended base; and E. anepoxidizing agent, present in about 0.6 to about 1.5 moles per unreactedsecondary or tertiary amino group remaining on the extended base, withthe proviso that the amount of epoxidizing agent is not sufficiently inexcess to reduce the pH of the reaction medium below about 5.0, selectedfrom at least one of the group consisting of epihalohydrins and alkylsubstituted epihalohydrins, with Ii. water, said resin being present inan amount of 70 parts by weight and said water being present in anamount of at least 30 parts by weight.
 20. Paper produced by the methodof claim 19.